CN1039306C - Ammonia-preparing technique from heavy oil - Google Patents

Ammonia-preparing technique from heavy oil Download PDF

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Publication number
CN1039306C
CN1039306C CN93101074A CN93101074A CN1039306C CN 1039306 C CN1039306 C CN 1039306C CN 93101074 A CN93101074 A CN 93101074A CN 93101074 A CN93101074 A CN 93101074A CN 1039306 C CN1039306 C CN 1039306C
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gas
steam
ammonia
unstripped gas
waste heat
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Expired - Fee Related
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CN93101074A
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CN1077175A (en
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张翊人
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CHINA WUHUAN CHEMICAL ENGINEERING Co
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CHINA WUHUAN CHEMICAL ENGINEERING Co
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/02Preparation, purification or separation of ammonia
    • C01C1/04Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engine Equipment That Uses Special Cycles (AREA)

Abstract

The present invention relates to a low-energy consumption ammonia-preparing technique for heavy oil. A gas turbine is utilized to replace a steam turbine and a power boiler system which are originally used so as to locally improve the flow, namely that a raw gas humidifying method is changed, a flue heater and a saturation section are arranged, and residual heat with lower level in off gas of the gas turbine is utilized to replace hypo-high pressure steam with higher energy level or heat with high level. The energy consumption is less than 34GJ when one ton of ammonia is produced by using the technique under the condition of basically not increasing investment, and the total oil consumption is from 910 to 990 kilograms. The present invention is also suitable for the production process of preparing synthetic gas by taking heavy oil or coal as raw materials with a partial oxidation method.

Description

With the mink cell focus is the method that cuts down the consumption of energy in the Ammonia Process of raw material
The invention belongs to system ammonification fertilizer technology class, belong to mink cell focus technique for production of ammonia class particularly.
Modern with the mink cell focus is, and raw material system ammonia is with vacuum residuum or heavy oil is raw material.The atomizing back is under the condition of 5-9MPa pressure and the existence of suitable quantity of water steam, carry out incomplete combustion and produce 1320-1380 ℃ high temperature with a certain amount of oxygen, and the unstripped gas and the small amounts of carbon black of hydrogen and carbon monoxide are rich in generation, spray into a large amount of hot water then and by below the Quench to 260 ℃, simultaneously gas is by humidification and most carbon black is captured by hot water, remove remaining solid impurities such as carbon black by the hot wash system again, enter shift conversion step again, promptly carbon monodixe conversion Cheng Qing and carbonic acid gas.Conversion gas is told carbonic acid gas and slough various impurity gas by cleaning sections such as low-temperature rectisol and liquid nitrogen washing again, and allocates an amount of pure nitrogen gas into and become purified synthesis gas containing nitrogen, at last synthetic ammonia under high pressure.Its typical technological process block-diagram is seen Fig. 1.The carbonic acid gas of by-product in ammonia and the production process, can be in urea plant urea synthesis.
Mink cell focus system ammonia needs a large amount of power to rotate various compressors and pump etc.Comprise urea production, required amount of power is generally 1300-1500KWh/t ammonia, the present situation of power resources is: in large-scale nitrogen fertilizer plant, large-scale high voltage power boiler systems (being fuel with mink cell focus mainly) and corresponding steam turbine are set, then almost all electricity consumptions in medium-sized ammonia factory.Ton ammonia energy consumption in the Ammonia Production: domestic large-scale factory is about 44GJ, and medium-sized factory then reaches 58GJ.
Adopt high voltage power boiler systems and the steam turbine source that is used as power, its power cycle as shown in Figure 2: the deoxidation feedwater pumps into the high voltage power boiler systems, makes the generation high pressure superheated steam with combusting heavy oil, again by steam turbine generation power.Air of using in the driving technological process and nitrogen compressor etc.The weary gas of the about 0.02MPa that discharges from steam turbine is condensed into water again by water coolant condenser.The efficient of this power cycle is not high, and effectively the hot merit transformation efficiency is difficult after deduction circulation consumable and the water coolant energy consumption surpasses 25%.
Internal combustion turbine belongs to internal combustion engine.Internal combustion turbine removes expansion working, exports outside the very big power, and still has 420-560 ° of temperature from the approaching non-pressurized weary gas (or flue gas) of turbine discharge, also contains the oxygen of 14-16%, can further utilize.
As far back as the sixties, (with the Sweet natural gas is raw material to the Braun technology of the U.S., produce synthetic ammonia with two sections steam reformings) just bring into use internal combustion turbine to drive the process air compressor, and replace the combustion air of first section steam reforming stove with the weary gas of discharging, obtain certain energy-saving effect, but technology not development again.So far yet there are no with coal or mink cell focus is the documents and materials of using gas turbine technology in the production technique of raw material system ammonia.
It is the method that cuts down the consumption of energy in the Ammonia Process of raw material with the mink cell focus that purpose of the present invention is intended to study a kind of, adopt present method introducing internal combustion turbine and replace original power boiler and steam turbine, basically do not increasing under the situation of investment, only former technological process is made local flow improvement, and a ton ammonia total energy consumption is dropped to less than 34GJ, thereby reach the energy-conservation effect of big spoke degree.
The objective of the invention is to realize in the following manner, with the mink cell focus is the method that cuts down the consumption of energy in the Ammonia Process of raw material, mink cell focus carries out incomplete combustion and generates unstripped gas and the small amounts of carbon black that is rich in hydrogen and carbon monoxide in vapourizing furnace, through Venturi scrubber, tell from hypomere and to contain grey hot water, incoming stock again gas wash tower, the flush away residual ash.The unstripped gas of drawing from unstripped gas washing tower top at saturated section by humidification and remove carbon black, import shift conversion step, promptly carbon monodixe conversion Cheng Qing and carbonic acid gas, conversion gas is told carbonic acid gas and is sloughed various impurity gas through low-temperature rectisol and liquid nitrogen washing cleaning section, and allocate an amount of nitrogen into and become purified synthesis gas containing nitrogen, synthetic ammonia under high pressure at last.The unstripped gas of drawing from unstripped gas washing tower top, heating also at saturated section by the hot water of being introduced from the top near boiling point, humidification then imports shift conversion step to containing steam 30-60%.The weary gas of internal combustion turbine is conducted to the combustion chamber, with nitrogen washing tail-gas and a small amount of mink cell focus mixed firing, the hot gas that comes out from the combustion chamber is used for the saturation steam of overheated technological process by-product earlier, flue well heater by the waste heat recovery section again, be used for other process streams of preheating then, make and be cooled to emptying below 175 ℃, mainly the hot water by the flue heater heats imports saturated section, the hot water major part of the lower temperature of discharging from saturated section below is circulated by recycle pump, small part is drawn toward the unstripped gas washing tower, make the make up water of carbon black extraction and washing system, after the waste heat of shift conversion step makes feedwater deoxidation and preheating, import the waste heat boiler of heavy oil gasifying operation and ammonia synthesis operation, and produce high-pressure saturated steam, by the heating coil in the waste heat recovery section by after overheated, lead toward steam turbine power takes place, be used for driving other compressors and the generator of technological process, and extract low pressure steam out and use by oneself, be condensed by condenser after unnecessary steam further expands for technological process.
Content of the present invention is described in detail in detail with reference to the accompanying drawings
Fig. 1 has mink cell focus Ammonia Process flow diagram now
Fig. 2 has the steam power cycle synoptic diagram now
Fig. 3 has the washing system synoptic diagram now
Fig. 4 washing of the present invention and saturation system schema
The waste heat recovery schema that machine fuel is distilled oil is fired in Fig. 5 the present invention
Fig. 6 combustion machine burning of the present invention is the waste heat recovery schema of unstripped gas
Replace steam turbine and power boiler system with internal combustion turbine, be more or less the same aspect investment, if simple the replacement, then energy-saving effect is not obvious.But the weary gas that internal combustion turbine is discharged still contains a large amount of available heat energy, if can be with it utilization rationally energy efficient effectively then, reduce production costs, based on this, the present invention has made local flow improvement to former technology: changed the humidification mode of unstripped gas, in the waste heat recovery section of the weary gas of internal combustion turbine the flue well heater has been set; Make mink cell focus pressurized gasification operation adopt the waste heat boiler flow process, the reaction heat in the ammonia synthesis process should be used for by-product high-pressure steam as far as possible and be not used in preboiler water, and the waste heat that fully reclaims shift conversion step is mainly used in the deoxidation and the preheating of feedwater.
Make two kinds of mode of unstripped gas humidification: the one, mink cell focus pressurized gasification operation adopts chilling process, unstripped gas after the Quench enters washing system shown in Figure 3, by I and II Venturi scrubber, unstripped gas washing tower, make about moisture content to 60%, directly enter shift conversion step; The one, adopt pot destroying process, the unstripped gas that has gone out useless pot and carried more solid impurity secretly also must pass through washing system, the unstripped gas of drawing from unstripped gas washing tower top only contains steam 22-25%, is originally to allocate sufficient steam into and enter shift conversion step, changes into now and enters shown in Figure 4 saturated section.Being heated also at saturated section unstripped gas by the hot water of introducing from the top near boiling point, humidification imports shift conversion step then to containing steam 50-60%.Saturated section top that preferably is located at the unstripped gas washing tower also can be designed side by side.
Fig. 4 flow process is to utilize internal combustion turbine to replace the higher sub-high pressure steam of energy level than the low level waste heat on effect, is used to take place power or does him use and vacate sub-high pressure steam; For chilling process, then be to utilize heat energy to replace high level heat than low level, in waste heat boiler, produce high pressure steam and vacate high level heat, be used to take place power or his usefulness, thereby reach remarkable energy saving effect.
The amount of power that the present invention is directly provided by internal combustion turbine with 500KWh/t ammonia about for good.Scheme is air compressor and the nitrogen compressor that drives the air separation operation with 2 internal combustion turbine respectively preferably, perhaps drives refrigerant condenser with a more small-sized internal combustion turbine again.The fuel of internal combustion turbine can directly use distilled oil, also can use the unstripped gas that is generated by heavy oil gasifying.
When fuel adopted distilled oil, internal combustion turbine waste heat recovery flow process as shown in Figure 5.The heat that is used for pre-thermal conversion recirculated water by this flow process accounts for about 40% of the weary total waste heat amount of gas of internal combustion turbine.This part heat originally be difficult to abundant recycling, and being utilized that the present invention is about to has reached energy-conservation effect because thermal potential is lower.
The unstripped gas that fuel adopts heavy oil gasifying to generate, internal combustion turbine waste heat recovery flow process as shown in Figure 6, its flow process and flow process shown in Figure 5 are similar, different is: because the raw gas pressure inlet pressure required far above internal combustion turbine, its unnecessary potential energy be should give recovery to improve the process total efficiency.The present invention makes earlier and is preheated to more than 330 ℃ by the coil pipe in the waste heat recovery section through the coarse raw materials gas that washs (desulfurization in case of necessity), is depressurized to a little more than the required pressure of internal combustion turbine by decompressor again, is re-used as fuel gas and introduces internal combustion turbine.The power that decompressor obtains is used for driving relatively large pump of technological process or generator.
Adopt the technology of the present invention, synthetic ton ammonia energy expenditure index sees the following form:
Starting material unit Fuel is distilled oil Fuel is unstripped gas
Unit consumption Energy consumption GI Unit consumption Energy consumption GJ
Crude fuel heavy oil t 0.732 30.810 0.933 39.270
Sealing diesel oil t 0.035 1.517 0.045 1.950
Petroleum naphtha t 0.144 6.482 0.007 0.315
Methyl alcohol kg 0.4 0.008 0.4 0.008
De-salted water t 3.0 0.022 3.0 0.022
Recirculated water t 232.8 0.682 264.5 0.775
Power KWh -255.6 -3.026 -366.6 -4.341
Steam (2.5MPa) t -1.32 -4.039 -1.32 -4.039
Add up to 32.456 33.960
When fuel is unstripped gas, though the cost of synthetic ammonia is lower, but increase the throughput about 30% of air separation, mink cell focus pressurized gasification, three operations of carbon black extraction because of need, make total system invest corresponding growth by 10%, for distillating the about 1.5GJ of innage, therefore adopt distilled oil is that fuel is comparatively desirable to ton ammonia energy consumption than fuel.
Adopt present technique synthetic ammonia, do not increasing under the situation of investment basically, make a production ton ammonia energy consumption reduce to 32.5GJ, 33.960GJ by 44GJ, total oil consumption is reduced to 911kg by the 1266kg of existing production equipment, real genus less energy-consumption technique for production of ammonia.
The present invention also be applicable to the mink cell focus be raw material produce synthetic gas so that produce Chemicals such as methyl alcohol, be that raw material adopts partial oxidation process to produce unstripped gas and then produce in the process of Chemicals such as nitrogen, methyl alcohol with the coal.

Claims (2)

1, with the mink cell focus is the method that cuts down the consumption of energy in the Ammonia Process of raw material, mink cell focus carries out incomplete combustion and generates unstripped gas and the small amounts of carbon black that is rich in hydrogen and carbon monoxide in vapourizing furnace, through Venturi scrubber, tell from hypomere and to contain grey hot water, incoming stock again gas wash tower, the flush away residual ash, the unstripped gas of drawing from unstripped gas washing tower top at saturated section by humidification and remove carbon black, import shift conversion step, promptly carbon monodixe conversion Cheng Qing and carbonic acid gas, conversion gas is told carbonic acid gas and is sloughed various impurity gas through low-temperature rectisol and liquid nitrogen washing cleaning section, and allocate an amount of nitrogen into and become purified synthesis gas containing nitrogen, synthetic ammonia under high pressure at last, it is characterized in that the unstripped gas of drawing from unstripped gas washing tower top, saturated section by introduced from the top near the hot water heating of boiling point and humidification to containing steam 50-60%, then import shift conversion step, the weary gas of internal combustion turbine is conducted to the combustion chamber, with nitrogen washing tail-gas and a small amount of mink cell focus mixed firing, the hot gas that comes out from the combustion chamber is used for the saturation steam of overheated technological process by-product earlier, flue well heater by the waste heat recovery section again, be used for other process streams of preheating then, make and be cooled to emptying below 175 ℃, mainly the hot water by the flue heater heats imports saturated section, the hot water major part of the lower temperature of discharging from saturated section below is circulated by recycle pump, small part is drawn toward the unstripped gas washing tower, make the make up water of carbon black extraction and washing system, after the waste heat of shift conversion step makes feedwater deoxidation and preheating, import the waste heat boiler of heavy oil gasifying operation and ammonia synthesis operation, and the generation high-pressure saturated steam, by the heating coil in the waste heat recovery section by after overheated, lead toward steam turbine power takes place, be used for driving other compressors and the generator of technological process, and extract low pressure steam out and use by oneself for technological process, after further expanding, unnecessary steam is condensed by condenser.
2,, it is characterized in that the fuel of internal combustion turbine can be the unstripped gas that generates behind distilled oil or the heavy oil gasifying according to the described method of claim.
CN93101074A 1993-02-02 1993-02-02 Ammonia-preparing technique from heavy oil Expired - Fee Related CN1039306C (en)

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CN1039306C true CN1039306C (en) 1998-07-29

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20021663A1 (en) * 2002-07-26 2004-01-26 Snam Progetti PROCEDURE FOR THE PRODUCTION OF SYNTHESIS GAS FROM HEAVY CHARGES SUCH AS HEAVY OILS AND DISTILLATION RESIDUES USING OXIDATION
US7503947B2 (en) * 2005-12-19 2009-03-17 Eastman Chemical Company Process for humidifying synthesis gas
AU2007328925B2 (en) * 2006-12-08 2010-12-02 Shell Internationale Research Maatschappij B.V. Process for producing a purified synthesis gas stream
CN101629085A (en) * 2008-09-24 2010-01-20 何巨堂 Method for designing driving system for circulating hydrogen compressor of hydrocarbon hydrogenation device
CN104560201B (en) * 2013-10-25 2017-07-21 昊华工程有限公司 The production technology and system and ammonia synthesis process and system of high-purity hydrogen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"合成氨工艺与节能" 1988.7.1 张成芳,华东化工学院出版社 *

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